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Abstract

A new Ce(III)-malonate, growth by hetero-nuclear synthesis, is investigated structurally at 100K. In this oxobridged material, the bi-anion does not allow the formation of any synthons, but various bridges form connections displaying typical sub-features. Cross-linked edge-shared CeO 9 and CeO 7 (H 2 O) 3 polyhedrons built up 3D packing accommodating two water molecules embedded in extensive H-bonds. Stable at 25°C, it undergoes concomitant dehydration and decarboxylation sequences. By comparison, Ca(II)-hydrogenmalonate and acidic Ba-malonate are also oxo-bridged polymers, but obtained differently and are much more stable. The former shows face-sharing binuclear units, and synthons. The protonated ligands present in the two alkaline-earth materials give peculiar decomposition process.Supporting information: TGA/ DTA/ DTTA curves of Cabased compound, TGA/ DTA/ DTTA curves of Ba-based compound, Coordination polyhedrons and fragment of 3D framework in Ce-malonate, Cross-linked layers in Ce-malonate, The C(6) synthons in Ca-based compound, The bi-polyhedron stacking in Ca-based compound, Crystal data, collection procedures and refinement for Ce-malonate, Selected geometric parameters in Ce coordination spheres, Hydrogen-bond geometry in Cemalonate, XRPD(X-ray powder diffraction) patterns of some intermediate and final TG products.